EP3093854B1 - Rechteckiger isolierter draht und stromgeneratorspule - Google Patents

Rechteckiger isolierter draht und stromgeneratorspule Download PDF

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Publication number
EP3093854B1
EP3093854B1 EP14877820.2A EP14877820A EP3093854B1 EP 3093854 B1 EP3093854 B1 EP 3093854B1 EP 14877820 A EP14877820 A EP 14877820A EP 3093854 B1 EP3093854 B1 EP 3093854B1
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EP
European Patent Office
Prior art keywords
layer
resin layer
extruded coating
thermoplastic resin
coating layer
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Application number
EP14877820.2A
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English (en)
French (fr)
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EP3093854A4 (de
EP3093854A1 (de
Inventor
Hideo Fukuda
Makoto Oya
Keisuke Ikeda
Satoko Yamoto
Tsuneo Aoi
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Essex Furukawa Magnet Wire Japan Co Ltd
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Essex Furukawa Magnet Wire Japan Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/308Wires with resins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00Insulated conductors or cables characterised by their form
    • H01B7/02Disposition of insulation
    • H01B7/0208Cables with several layers of insulating material
    • H01B7/0225Three or more layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00Insulated conductors or cables characterised by their form
    • H01B7/02Disposition of insulation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60LPROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00Electric propulsion with power supplied within the vehicle
    • B60L50/10Electric propulsion with power supplied within the vehicle using propulsion power supplied by engine-driven generators, e.g. generators driven by combustion engines
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/301Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen or carbon in the main chain of the macromolecule, not provided for in group H01B3/302
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/306Polyimides or polyesterimides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/36Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes condensation products of phenols with aldehydes or ketones
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/421Polyesters
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00Insulated conductors or cables characterised by their form
    • H01B7/0009Details relating to the conductive cores
    • H01B7/0036Alkali metal conductors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00Insulated conductors or cables characterised by their form
    • H01B7/02Disposition of insulation
    • H01B7/0275Disposition of insulation comprising one or more extruded layers of insulation
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02KDYNAMO-ELECTRIC MACHINES
    • H02K3/00Details of windings
    • H02K3/02Windings characterised by the conductor material
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02KDYNAMO-ELECTRIC MACHINES
    • H02K3/00Details of windings
    • H02K3/04Windings characterised by the conductor shape, form or construction, e.g. with bar conductors
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02KDYNAMO-ELECTRIC MACHINES
    • H02K3/00Details of windings
    • H02K3/30Windings characterised by the insulating material
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02KDYNAMO-ELECTRIC MACHINES
    • H02K3/00Details of windings
    • H02K3/32Windings characterised by the shape, form or construction of the insulation

Definitions

  • the present invention relates to an insulated wire obtained by coating a metal conductor with a resin, and particularly relates to an insulated wire used as a coil of an electric generator installed in, for example, electric power-driven vehicles.
  • a round wire or a rectangular wire is employed as an insulated wire (magnet wire) used for a stator of an electric generator (motor generator) installed in automobiles.
  • a fill factor of the stator can be increased as compared to a case where a conductor having a generally round cross section is employed, and thus an electric generator having a reduced size and a higher power can be obtained.
  • an insulated wire of the generator for vehicles is required to have properties, such as an insulating property, resistance to thermal softening, flexibility, and a long-term heat resistance, which are improved as compared to those of a conventional configuration.
  • a so-called enameled wire having a rectangular conductor and an insulating layer of a thermosetting resin such as polyamide-imide (PAI) formed thereon is often used as a stator coil.
  • PAI polyamide-imide
  • an enamel coating alone does not provide sufficient reliability to high voltage. Accordingly, in order to improve the reliability to high voltage, attempts have been made to form another insulating layer on an outside of the enameled wire.
  • some insulated wires have, on an outside of the enameled wire, another insulating layer formed of an amorphous resin such as polyethersulfone (PES).
  • PES polyethersulfone
  • an insulating layer having excellent long-term heat resistance and insulating properties at a high voltage can be obtained.
  • an amorphous resin such as PES is poor in chemical resistance. Therefore, when a coil is formed by winding an insulated wire and immersed into an impregnating varnish such as an epoxy resin, and thereafter, upon curing the impregnating varnish, the insulating layer formed of an amorphous resin is affected by the impregnating varnish and a crack tend to occur in the insulating layer.
  • an insulated wire which is further provided with an insulating layer formed of a crystalline resin such as polyphenylene sulfide (PPS) or polyetheretherketone (PEEK) on an outside of the aforementioned insulating layer formed of an amorphous resin.
  • a crystalline resin such as polyphenylene sulfide (PPS) or polyetheretherketone (PEEK)
  • PPS polyphenylene sulfide
  • PEEK polyetheretherketone
  • an insulated wire has, on an outside of the enameled wire, a lower layer formed of PES and an upper layer formed on an outer surface of the lower layer, with the upper layer being formed of a polymer alloy of PES and PPS or of PES and PEEK ( Japanese Laid-Open Patent Publication No. 2010-123390 ).
  • the upper layer is formed of a polymer alloy containing PES, adhesion with the lower layer formed of PES improves. Thus, occurrence of peeling between the upper layer and the lower layer which may occur in a bending process can be suppressed.
  • EP 3 089 169 A1 describes an insulated wire, having a thermosetting resin covering, directly or by interposing an insulating layer, on a rectangular conductor, and a thermoplastic resin covering on a periphery of the thermosetting resin covering, wherein the thermoplastic resin covering has at least two layers of the thermoplastic resin layers, and the thermoplastic resin layers adjacent to each other are formed of thermoplastic resins different from each other.
  • EP 2 328 154 A1 teaches an inverter surge-resistant insulated wire, having an enamel baked layer, an adhesive layer, and an extrusion-coated resin layer, around the outer periphery of a conductor.
  • EP 0 944 099 A1 describes a multilayer insulated wire having two or more extrusion-coating insulating layers provided on a conductor directly or via some other layer, or provided on the outside of a multicore wire composed of conductor cores or insulated cores that are collected together, wherein at least one of the insulating layers is made of a mixture prepared by mixing 100 parts by weight of a polyethersulfone resin and 10 to 100 parts by weight of an inorganic filler.
  • JP 2013 041700 A discloses an insulated wire having a conductor and a baked enamel layer containing at least a polyamide-imide provided on the outer periphery of the conductor where an extrusion-coated resin layer is provided on the outer periphery of the baked enamel layer.
  • EP 3 089 170 A1 describes a multilayer insulated wire having a polyester-based resin layer formed of a polyester-based resin containing at least a trihydric or higher hydric alcohol constituent on a conductor, and a PEEK resin layer formed of polyether ether ketone or modified polyether ether ketone, directly or by interposing an intermediate layer, on the polyester-based resin layer.
  • the present inventors carried out assiduous studies to attain the above object, and as a result, reached the findings that, by forming a single or a plurality of thermoplastic resin layers on an enamel layer and specifying the range/ranges of relative crystallinity of the thermoplastic resin layer/layers formed on the enamel layer, adhesion between insulating layers and prevention of occurrence of a crack can be achieved together, and that, further, an excellent ATF-resistant property can be obtained.
  • the present invention was made based on such findings.
  • thermoplastic resin layer a plurality of thermoplastic resin layers are formed on a thermosetting resin layer, and with an adhesion strength between the thermosetting resin layer and the thermoplastic resin layer being 50 gf/mm to 100 gf/mm, moderate adhesion can be obtained between the thermosetting resin layer and the thermoplastic resin layer, and occurrence of a crack extending from the thermoplastic resin layer and reaching an outer surface of the rectangular conductor can be prevented. Accordingly, both an improvement in adhesion and prevention of occurrence of a crack can be achieved by suppressing the adhesion strength between the thermosetting resin layer and the thermoplastic resin layer from increasing higher than required, and it is possible to improve flex resistance reliability. Also, since the thermoplastic resin layer is disposed at an outer most layer, it has an excellent chemical resistance and, particularly, an excellent ATF-resistant property.
  • an adhesion strength between a first thermoplastic resin layer and a second thermoplastic resin layer formed on the first thermoplastic resin layer is 50 gf/mm to 100 gf/mm.
  • the first thermoplastic resin layer is formed on the thermosetting resin layer, and the first thermoplastic resin layer has a relative crystallinity of greater than or equal to 20% and less than or equal to 50%, and preferably greater than or equal to 30% and less than or equal to 50%, the relative crystallinity being calculated based on heat of fusion and heat of crystallization measured by differential scanning calorimetry.
  • both an improvement in adhesion and prevention of occurrence of a crack can be achieved by suppressing the adhesion strength between the thermosetting resin layer and the first thermoplastic resin layer from increasing higher than required, while maintaining the flexibility and resistance to thermal softening, and it is possible to improve flex resistance reliability.
  • the first thermoplastic resin layer is disposed at an outer most layer, it has an excellent chemical resistance and, particularly, an excellent ATF-resistant property.
  • the adhesion strength between the thermosetting resin layer and the first thermoplastic resin layer is 50 gf/mm to 100 gf/mm, moderate adhesion can be obtained between the thermosetting resin layer and the first thermoplastic resin layer, and occurrence of a crack extending from the first thermoplastic resin layer and reaching an outer surface of the rectangular conductor can be prevented.
  • the second thermoplastic resin layer has a relative crystallinity which is approximately the same as or greater than the relative crystallinity of the first thermoplastic resin layer.
  • an adhesion strength between the first thermoplastic resin layer and the second thermoplastic resin layer can be 50 gf/mm to 100 gf/mm.
  • an adhesion strength between the first thermoplastic resin layer and the second thermoplastic resin layer can be 50 gf/mm to 100 gf/mm.
  • FIGs. 1A and 1B are diagrams schematically showing a configuration of a rectangular insulated wire according to an embodiment of the present invention, of which Fig. 1A is a perspective diagram and Fig. 1B is a partial cross-sectional view.
  • FIGS. 1A and 1B are diagrams schematically showing a configuration of a rectangular insulated wire according to an embodiment of the present invention, of which Fig. 1A is a perspective diagram and Fig. 1B is a partial cross-sectional view. Length, width and thickness of each configuration in FIGS. 1A and 1B are shown by way of example, and length, width and thickness of each configuration in the rectangular insulated wire of the present inventions should not be limited to those illustrated in FIGS. 1A and 1B .
  • a rectangular insulated wire 1 shown in FIGS. 1A and 1B includes, as described above as the first invention, a rectangular conductor 2 having a generally rectangular cross section, a thermosetting resin layer 3 formed to cover the rectangular conductor, a thermoplastic resin layer 4 formed to cover the thermosetting resin layer, and a thermoplastic resin layer 5 formed to cover the thermoplastic resin layer 4, and is further characterized in that an adhesion strength between a thermosetting resin layer and a first thermoplastic resin layer and an adhesion strength between a first thermoplastic resin layer and a second thermoplastic resin layer are controlled to be in a predetermined range.
  • the example includes, as coating layers, a thermosetting resin layer and also two thermoplastic resin layers of different relative crystallinities, and is characterized in that the thermoplastic resin layer 5 has a relative crystallinity greater than that of the thermoplastic resin layer 4.
  • the relative crystallinities of these thermoplastic resin layers will be described in more detail below.
  • the size of the conductor is determined depending on application, and thus not particularly specified, but it is preferable that the rectangular conductor 2 has, in its cross section, a ratio of a short side to a long side (short side: long side) of 1:1 to 1:4.
  • the long side is preferably 1.0 mm to 5.0 mm.
  • the short side is preferably 0.4 mm to 3.0 mm, and more preferably, 0.5 mm to 2.5 mm.
  • the range of conductor size with which an effect of the inventions can be obtained is not limited thereto.
  • a rectangular cross section is more common as compared to a square cross section, but the cross sectional shape also differs depending on the application.
  • such rectangular conductor 2 may be chamfered at four corners of a cross section of the conductor (radius of curvature r), and a smaller "r” is preferable for the purpose of increasing the fill ratio of the conductor in a stator slot, and a greater "r” is preferable for the purpose of suppressing partial discharge phenomenon due to electric field convergence at the four corners.
  • the radius of curvature r is preferably 0.6 mm or less, and more preferably 0.2 mm to 0.4 mm.
  • the range within which an effect of the inventions can be achieved is not limited thereto.
  • the rectangular conductor 2 is made of a metal having conductivity, and a material thereof may be any material having conductivity, and may be made of, for example, aluminum or aluminum alloy, or copper or copper alloy.
  • the material may be a 1000 series alloy having a low strength but a high aluminum ratio or an Al-Mg-Si based alloy such as, for example, a 6101 alloy, which is a 6000 series aluminum alloy.
  • aluminum or aluminum alloy has a conductivity of about two-thirds of the conductivity of copper or copper alloy, its specific gravity is about one-third thereof.
  • a coil can be light weighted and can contribute to the light weighting of the vehicle and improvement in fuel consumption.
  • the rectangular conductor 2 is formed of copper or copper alloy
  • those used in conventional insulated wires may be used.
  • those formed of low oxygen copper with an oxygen content of less than or equal to 30 ppm, and further preferably low oxygen copper with an oxygen content of less than or equal to 20 ppm or oxygen-free copper are used.
  • oxygen content of less than or equal to 30 ppm even if the conductor is caused to melt by heat for welding, voids due to contained oxygen do not occur at a welded portion and thus a decrease in electric resistance at the welded portion can be prevented, and strength at the welded portion can be maintained.
  • the thermosetting resin layer 3 is a baked enamel layer formed by baking a resin varnish applied to the rectangular conductor 1 and has a thickness of 20 ⁇ m to 60 ⁇ m.
  • Such baked enamel layer may be a single layer or a plurality of such baked enamel layers may be provided.
  • each layer includes a resin as a major component and additives as a minor component, and the resin is the same as or different from that of other layers, and the additives are the same as or different from those of other layers.
  • the baked enamel layer/layers may be formed directly on an outer peripheral surface of the rectangular conductor or via other layer having an insulating property.
  • the enamel layer has a thickness of less than or equal to 60 ⁇ m, and further preferably less than or equal to 55 ⁇ m. Further, it is preferable that the enamel layer has a certain thickness, so as not to impair a withstand voltage property and a heat resistant property, which are properties necessary for an enameled wire to be used as the insulated wire.
  • the thickness of the enamel layer should not be particularly limited as long as it is a thickness that does not produce pinholes, and preferably greater than or equal to 10 ⁇ m, and further preferably, greater than or equal to 20 ⁇ m.
  • the resin varnish includes a resin as its major component, and in terms of a heat resistance property, the resin is composed of, for example, one or more of polyamide-imide (PAI), polyesterimide, polyimide (PI), class H polyester (HPE) and polyetherimide (PEI), and particularly, polyamide-imide, polyimide or class H polyester is preferable.
  • PAI polyamide-imide
  • PI polyimide
  • HPE class H polyester
  • PEI polyetherimide
  • Class H polyester refers to polyester that is categorized into a heat-resistant class of class H.
  • the resin varnish includes an organic solvent that is used for making a thermosetting resin into a varnish.
  • the organic solvent is not particularly limited as long as it does not inhibit the reaction of the thermosetting resin, and, for example, the organic solvent may be: amide solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAC), dimethylsulfoxide, and N,N-dimethylformamide; urea solvents such as N,N-dimethylethylene urea, N,N-dimethylpropylene urea, and tetramethylurea; lactone solvents such as ⁇ -butyrolactone and ⁇ -caprolactone; carbonate solvents such as propylene carbonate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as such as ethylacetate, n-butyl acetate, butyl cello
  • amide solvents and urea solvents are preferable in terms of properties such as a high dissolving property and a high reaction accelerating property, and N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylethylene urea, N,N-dimethylpropylene urea, and tetramethylurea are more preferable since these do not have hydrogen atoms which are likely to inhibit crosslinking reactions by heating, and N-methyl-2-pyrrolidone is preferable.
  • Additives which are minor components of the resin varnish include, for example, antioxidant, antistatic agent, ultra-violet light inhibitor, light stabilizer, fluorescent whitening agent, pigment, dye, compatibilizer, lubricant, strengthening agent, flame retardant, crosslinking agent, crosslinking assistant, plasticizer, viscosity-increasing agent, viscosity-reducing agent and elastomer.
  • the resin varnish including components as described above may be, for example, applied to a rectangular conductor using a varnish-applying die having a shape similar to the shape of the conductor, and in a case where the cross-sectional shape of the conductor is quadrangular, the resin varnish may be applied using a die called "a universal die" having a cross sectional geometry in which two pairs of parallel lines are arranged perpendicular to each other.
  • the conductor having the resin varnish applied thereon is baked in a baking furnace. For example, using a free convection-type vertical furnace having a length of approximately 5 m to 8 m, the process may be performed continuously at 400 °C to 500 °C with a passage time of 10 to 90 seconds.
  • the adhesion strength at an inner portion of the thermosetting resin layer may be controlled by modifying the configuration and the type of films at an inner portion of the thermosetting resin layer.
  • the thermoplastic resin layer 4 is a coating layer of crystalline resin having a thickness of 20 ⁇ m to 200 ⁇ m, specifically, an extruded coating layer that coats the baked enamel layer by extrusion.
  • the extruded coating layer is preferably formed of a crystalline resin, and, for example, formed of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketone (PEK), polyphenylene sulfide (PPS) or thermoplasticity polyimide (PI).
  • the extruded coating layer has a thickness of less than or equal to 200 ⁇ m, and more preferably, less than or equal to 180 ⁇ m to achieve an effect of the invention.
  • a white colored portion may be produced at a surface of the insulated wire when the insulated wire is wound around an iron core and heated, independent of the rate of a film crystallinity of the extruded coating layer to be described below.
  • the extruded coating layer is excessively thick, the extruded coating layer itself has rigidity, and thus lacks flexibility as an insulated wire, and there is a possibility that a problem in maintaining an electrically insulating property before and after the processing may arise.
  • the thickness of the extruded coating layer is preferably greater than or equal to 10 ⁇ m, and more preferably, greater than or equal to 20 ⁇ m.
  • thermoplastic resin layer 4 In a case where the thermoplastic resin layer 4 is formed by extrusion, it does not need to be passed through a baking furnace in the fabricating process, and thus the thickness of the insulating layer can be increased without increasing the thickness of an oxide film of the conductor.
  • the adhesion strength at an interface between them is set to be within a range of 50 gf/mm to 100 gf/mm. Thereby, occurrence of a crack progressing from the thermoplastic resin layer to an outer surface of the rectangular conductor can be prevented.
  • the adhesion strength between the thermosetting resin layer 3 and the thermoplastic resin layer 4 is less than 50 gf/mm, peeling is likely to occur between the thermosetting resin layer and the thermoplastic resin layer when the rectangular insulated wire is bent, and when the adhesion strength exceeds 100 gf/mm, the aforementioned crack is likely to occur.
  • the adhesion strength can be controlled to be 50 gf/mm to 100 gf/mm by applying plasma treatment and corona treatment to an interface between the thermosetting resin layer 3 and the thermoplastic resin layer 4 or - and not covered by the present invention - by making the crystallinity of the thermoplastic resin layer greater than or equal to 20% and less than or equal to 50%.
  • Plasma treatment may be an atmospheric pressure plasma treatment method.
  • Argon-oxygen mixed gas is used for creating plasma.
  • a corona processing device may employ a high frequency corona discharge treatment method.
  • a high frequency corona discharge treatment method In general, an output power of 500W and an output frequency of 20 kHz are used.
  • the thermoplastic resin layer 5 is an extruded coating layer that coats the thermoplastic resin layer 4 by extrusion.
  • the thermoplastic resin layer 4 and the thermoplastic resin layer 5 form a double-layered configuration, and the total thickness of the thermoplastic resin layer 4 and the thermoplastic resin layer 5 is preferably less than or equal to 200 ⁇ m for an upper limit of the total thickness of the two layers and preferably greater than or equal to 20 ⁇ m for a lower limit thereof, for the similar reason as the reason of determining the thickness of the thermoplastic resin layer for the above-mentioned case in which the extruded coating layer has a single layered configuration. Therefore, it is desirable to determine the total thickness range of the two layers to be within the range of 20 ⁇ m to 200 ⁇ m.
  • the extruded coating layer is made of a crystalline resin, and, for example, it is made of one of polyphenylene sulfide (PPS), polyetherketoneketone (PEEK) or polyetherketone (PEK). It is desirable for thermoplastic resin layer 5 to be formed of a crystalline resin which is the same as the thermoplastic resin layer 4, but may be formed of a different crystalline resin.
  • the adhesion strength between the thermoplastic resin layer 4 and the thermoplastic resin layer 5 is within the range of 50 gf/mm to 100 gf/mm. Thereby, occurrence of a crack from the thermoplastic resin layer to an outer surface of the rectangular conductor can be prevented. In a case where the adhesion strength between the thermoplastic resin layer 4 and the thermoplastic resin layer 5 is less than 50 gf/mm, peeling is likely to occur between two thermoplastic resin layers during flexure of the rectangular insulated wire. In a case where the adhesion strength exceeds 100 gf/mm, the aforementioned crack is likely to occur.
  • thermoplastic resin layer 4 and the thermoplastic resin layer 5 are resin of the same type, or a combination of resins of similar structures of polyketones such as PEEK, PEKK and PEK, the adhesion strength becomes higher than the case in which the resins are of different types.
  • thermoplastic resin layer since it is necessary to control the value of relative crystallinity, it is preferable to use a crystalline resin with which relative crystallinities of the first thermoplastic resin layer and the second thermoplastic resin layer can be controlled to be within the range of the present invention.
  • thermoplastic resin layer 4 relative crystallinity calculated based on heat of fusion and heat of crystallization measured by differential scanning calorimetry (DSC) is greater than or equal to 20% and less than or equal to 50%. That is, the relative crystallinity in the present invention is a relative ratio when the theoretically achievable maximum value of crystallinity is taken as 100%.
  • relative crystallinity heat of fusion ⁇ heat of crystallization / heat of fusion ⁇ 100 % , where
  • the adhesion strength between the thermosetting resin layer 3 and the thermoplastic resin layer 4 can be suppressed from increasing more than required, and while maintaining adhesion between the thermosetting resin layer 3 and the thermoplastic resin layer 4, occurrence of a crack extending from an outer surface of thermoplastic resin layer 4 to an outer surface of the rectangular conductor 2 can be prevented.
  • the relative crystallinity exceeds 50%, adhesion between the thermosetting resin layer 3 and the thermoplastic resin layer 4 decreases, and peeling is more likely occur between the layers.
  • the adhesion strength between the thermosetting resin 3 and the thermoplastic resin 3 is 50 gf/mm to 100 gf/mm. Note that, because of the manufacturing method, even if time taken until water cooling is shortened as much as possible, a wire having a relative crystallinity of less than 20% cannot be manufactured.
  • the relative crystallinity of the second thermoplastic resin layer is almost the same as the relative crystallinity of the first thermoplastic resin layer, or greater than the relative crystallinity of the first thermoplastic resin layer. The reason for this is to improve scratch resistance and ATF-resistant property while maintaining the adhesion of the first thermoplastic resin layer and the second thermoplastic resin layer.
  • the relative crystallinity of the thermoplastic resin layer 5 based on the DSC measurement is substantially the same or different from the relative crystallinity of the thermoplastic resin layer 4. Specifically, the relative crystallinity of thermoplastic resin layer 5 is 45% to 100% and within a range of -5% to 60% with respect to the relative crystallinity of the thermoplastic resin 4.
  • the relative crystallinity of the thermoplastic resin layer 5 is the same as or higher than the relative crystallinity of the thermoplastic resin layer.
  • the relative crystallinity of the thermoplastic resin layer 5 is somewhat high, an adhesion strength in the range of 50 gf/mm to 100 gf/mm can be obtained between the thermoplastic resin layer 5 and the thermoplastic resin layer 4.
  • thermoplastic resin layer 5 In a case where the relative crystallinity of the thermoplastic resin layer 5 is higher than the relative crystallinity of the thermoplastic resin layer 4, there is a concern on characteristics such as flexibility and resistance to thermal softening, but since the relative crystallinity of the thermoplastic resin layer 4 is greater than or equal to 20% and less than or equal to 50%, flexibility and resistance to thermal softening of the rectangular insulated wire 1 can be almost maintained.
  • chemical resistance, particularly ATF-resistant property can be further improved while suppressing an occurrence of partial discharge, and scratch resistance can also be improved.
  • thermoplastic resin layer is provided on the thermosetting resin layer, and the relative crystallinity in the vicinity of an interface between the thermoplastic resin layer and the thermosetting resin layer is greater than or equal to 20% and less than or equal to 50%.
  • a rectangular insulated wire which is obtained by coating a rectangular conductor was described by way of example, but it is not limited thereto, and may be a round insulated wire that is obtained by coating a conductor having a substantially round shaped cross section.
  • a rectangular winding is held in air at ordinary temperature for 1 to 4 seconds; in order to obtain a resin having a relative crystallinity in the range of from 70% to 90%, after coating by extrusion and until water cooling, the rectangular insulated wire is held in air at ordinary temperature for 6 to 7 seconds; and in order to obtain a resin having a relative crystallinity of over 90% and up to 100%, after coating by extrusion until water cooling, the rectangular insulated wire is held in air at ordinary temperature for 8 to 10 seconds.
  • thermoplastic resin layer a single extruded coating layer (thermoplastic resin layer) is provided.
  • a rectangular conductor copper with an oxygen content of 15 ppm
  • thermosetting resin polyamide-imide resin varnish (manufactured by Hitachi Chemical Company Ltd., product name "HPC-9000”) was used, and the resin was coated on the conductor using a die having a geometry similar to the shape of the conductor.
  • the coated conductor was caused to pass through a baking furnace set at 450 °C and having a furnace length of 8 m with a speed such that baking time is 15 seconds, to thus form an enamel layer of thickness 5 ⁇ m by this single baking step.
  • a baking furnace set at 450 °C and having a furnace length of 8 m with a speed such that baking time is 15 seconds, to thus form an enamel layer of thickness 5 ⁇ m by this single baking step.
  • an enamel layer of thickness 20 ⁇ m was formed and an enameled wire (thermosetting resin layer) having a coating thickness of 20 ⁇ m was obtained.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • thermoplastic PI manufactured by Mitsui Chemicals, Inc., product name "AURUM PL450C"
  • AURUM PL450C thermoplastic PI
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • water cooling was performed after a time interval of six seconds to form an extruded coating resin layer having a thickness of 75 ⁇ m outside the enamel layer.
  • an insulated wire was manufactured by a method similar to the method of Example 1.
  • Example 2 The same materials and method as Example 1 are used for manufacturing until the first extruded coating layer (extruded coating layer 1) is formed, and thereafter, as a second extruded coating layer, PEEK is used, and in order to provide an extruded resin layer having a relative crystallinity of 100%, after having performed extrusion coating of the PEEK using an extruding die, water cooling was performed after a time interval of eight seconds to form an extruded coating layer (extruded coating layer 2) having a thickness of 20 ⁇ m outside the first extruded coating layer.
  • an insulated wire made of an extruded coating enameled wire having a total thickness of (a sum of the thickness of the enamel layer and the two extruded coating resin layer) 60 ⁇ m was obtained.
  • Example 15 Except that the manufacturing was carried out using the same materials and method as Example 2 until the first extruded coating layer is formed, and further, the second extruded coating layer is modified to have a relative crystallinity of 95% and a thickness of 40 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • Example 15 Except that the manufacturing was carried out using the same materials and method as Example 3 until the first extruded coating layer is formed, and further, the second extruded coating layer is modified to have a relative crystallinity of 100% and a thickness of 45 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • Example 15 Except that the manufacturing was carried out using the same materials and method as Example 4 until the first extruded coating layer is formed, and further, the second extruded coating layer is modified to have a relative crystallinity of 85% and a thickness of 38 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • Example 15 Except that the manufacturing was carried out using the same materials and method as Example 5 until the first extruded coating layer is formed, and further, the second extruded coating layer is modified to have a relative crystallinity of 50% and a thickness of 50 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • Example 15 Except that the manufacturing was carried out using the same materials and method as Example 6 until the first extruded coating layer is formed, and further, the second extruded coating layer is modified to have a relative crystallinity of 45% and a thickness of 50 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • Example 15 Except that the manufacturing was carried out using the same materials and method as Example 7 until the first extruded coating layer is formed, and further, the second extruded coating layer is modified to have a relative crystallinity of 70% and a thickness of 50 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • Example 8 Except that the manufacturing was carried out using the same materials and method as Example 8 until the first extruded coating layer is formed, and further, the second extruded coating layer is modified to employ PEK and to have a relative crystallinity of 85% and a thickness of 55 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • Example 9 Except that the manufacturing was carried out using the same materials and method as Example 9 until the first extruded coating layer is formed, and further, the second extruded coating layer is modified to have a relative crystallinity of 90% and a thickness of 60 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • Example 15 Except that the manufacturing was carried out using the same materials and method as Example 10 until the first extruded coating layer is formed, and further, the second extruded coating layer is modified to have a relative crystallinity of 83% and a thickness of 65 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • the manufacturing was carried out using the same materials and method as Example 11, and further, the second extruded coating layer is modified to have a relative crystallinity of 90% and a thickness of 85 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • the manufacturing was carried out using the same materials and method as Example 12, and further, the second extruded coating layer is modified to employ thermoplastic PI as the resin, and to have a relative crystallinity of 75% and a thickness of 80 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • the manufacturing was carried out using the same materials and method as Example 13, and further, the second extruded coating layer is modified to have a relative crystallinity of 90% and a thickness of 80 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • the manufacturing was carried out using the same materials and method as Example 14, and further, the second extruded coating layer is modified to employ PPS as the resin and to have a relative crystallinity of 50% and a thickness of 85 ⁇ m, an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • the enameled layer is modified to have a thickness of 20 ⁇ m
  • the first extruded coating layer is modified to have a thickness of 95 ⁇ m
  • the second extruded coating layer is modified to have a relative crystallinity of 90% and a thickness of 95 ⁇ m
  • the first extruded coating layer is modified to have a thickness of 105 ⁇ m
  • the second extruded coating layer is modified to have a relative crystallinity of 45% and a thickness of 85 ⁇ m
  • an insulated wire was obtained by forming the second extruded coating layer similarly to Example 18.
  • the second extruded coating layer (extruded coating layer 2) was formed with the same materials and method as Example 22, and thereafter, as a third extruded coating layer, PEEK is used, and in order to form an extruded resin layer having a relative crystallinity of 90%, after having performed extrusion coating of the PEEK using an extruding die, water cooling was performed after a time interval of five seconds to form an extruded coating layer (extruded coating layer 3) having a thickness of 60 ⁇ m outside the second extruded coating layer. In this manner, an insulated wire having a total thickness of (a sum of the thickness of the enameled wire and the three extruded coating resin layer) 245 ⁇ m was obtained.
  • the first extruded coating layer is modified to employ PEI as the resin and to have a thickness of 10 ⁇ m
  • the second extruded coating layer is modified to have a relative crystallinity of 95% and a thickness of 100 ⁇ m
  • the enameled layer is modified to have a thickness of 35 ⁇ m
  • the first extruded coating layer is modified to have a relative crystallinity of 80% and a thickness of 75 ⁇ m
  • the second extruded coating layer is modified to have a relative crystallinity of 90% and a thickness of 80 ⁇ m
  • an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • the first extruded coating layer is modified to employ PES (manufactured by Sumitomo Chemical Co., Ltd., product name "SUMIKAEXCEL 4100G") as the resin and to have a thickness of 50 ⁇ m
  • the second extruded coating layer is modified to employ a polymer alloy of PES and PEEK (weight ratio 70:30) as the resin and to have a relative crystallinity of 65% and a thickness of 50 ⁇ m
  • an insulated wire was obtained by forming the second extruded coating layer similarly to Example 15.
  • thermosetting resin layer and the extruded coating layer and between the extruded coating layers a method of measuring the relative crystallinity, the adhesion strengths between the thermosetting resin layer and the extruded coating layer and between the extruded coating layers, presence or absence of a crack reaching the conductor, presence or absence of the peeling between the thermosetting resin layer and the extruded coating layer and between the extruded coating layers, and a method of measuring an ATF-resistant property will be described.
  • an electric wire sample from which only the extruded coating layer of the insulated wire is partly peeled was set to a tensile testing machine (manufactured by Shimadzu Corporation, device name "Autograph AG-X”), and the extruded coating layer was peeled off upwardly at a rate of 4 mm/min (180 degrees peeling). The tensile load thus read was taken as the adhesion strength.
  • the film crystallinity of the extruded coating resin layer of the present invention was measured as follows by differential scanning calorimetry (DSC) using a thermal analysis device (manufactured by Shimadzu Corporation, device name "DSC-60"). That is, 10 mg of the film of the extruded coating resin layer was collected and the temperature was raised at a rate of 5°C /min.
  • heating value (heat of fusion) due to fusion observed in region around 300 °C and heating value (heat of crystallization) due to crystallization observed around 150 °C were calculated and a value obtained by subtracting the heat of crystallization from the heat of fusion to the heat of fusion and by dividing the thus obtained difference by the heat of fusion was taken as the film crystallinity.
  • the insulated wire was cut into a 300 mm straight piece, and a scratch having a depth of approximately 10 ⁇ m was made at a central portion of the wire in a direction perpendicular to the longitudinal direction of the wire using a special jig. Then, placing the scratch at a peak, it was bent through 180° about a 1.0 mm iron core. Thereafter, presence or absence of a crack occurring near the peak was visually observed.
  • the insulated wire was cut into a 300 mm straight piece, and bent through 180° about a 1.0 mm iron core. Thereafter, presence or absence of a crack occurring between respective layers near the peak was visually observed.
  • the insulated wire was cut into a 300 mm straight piece, and placed in a sealed container made of SUS. 1,300 g ATF oil and 6.5 ml water (equivalent to 0.5% by weight) were placed into the container, and, were heated together with the sealed container made of SUS at 150° for 500 hours. After heat treatment, the insulated wire was removed and left until it reached an ordinary temperature. After reaching an ordinary temperature, it was bent through 180° about a 1.0 mm iron core. The sample subjected to the bending process was evaluated, and determined as a pass " ⁇ " if no crack extending from the extruded coating layer to the conductor has occurred, and determined as a fail" ⁇ " if a crack has occurred.
  • the extruded coating layer for this case has a relative crystallinity of 30% to 50% and in which the extruded coating layer is controlled to have a relative crystallinity in the above range results in the aforementioned results in which the flex resistance reliability and ATF resistant property are excellent.
  • the relative crystallinity in the resin increases, an increase in adhesion can be suppressed, and it can be considered that the reason for this is that, by increasing an amount of crystalline portions, they are intertwined with each other and an amount of amorphous portions that increases adhesion can be decreased, and as a result, that the adhesion can be controlled to be within a predetermined range.
  • Comparative Example 1 in which the resin of the extruded coating layer was PEI, the adhesion strength between the thermosetting resin layer and the extruded coating layer was 115 gf/mm and a crack extending from the extruded coating layer and reaching the conductor occurred.
  • Comparative Example 2 in which the extruded coating layer had a relative crystallinity of 80%, the adhesion strength between the thermosetting resin layer and the extruded coating layer was 40 gf/mm and peeling occurred between the thermosetting resin layer and the extruded coating layer.
  • Comparative Example 3 the extruded coating layer was not provided on the enameled wire, and an ATF-resistant property was poor.
  • Table 2 shows results of measurements and evaluations using the aforementioned method for Examples 15 to 32 and Comparative Examples 4 to 6.
  • EXAMPLE 15 EXAMPLE 16
  • EXAMPLE 17 EXAMPLE 18
  • EXAMPLE 19 EXAMPLE 20
  • EXAMPLE 21 EXAMPLE 22
  • EXAMPLE 23 EXAMPLE 24
  • Thermosetting resin layer PAI PAI PAI PAI PAI PI HPE PAI [Thickness : um] 20 30 60 50 50 60 50 55 50 40 20 Extruded coating layer 1 PEEK PEEK PEEK PEKK PPS PEEK Thermoplastic PI PEEK PEEK PEKK PEKK [Relative crystallinity: %] 45 25 40 42 45 50 50 45 45 25 45 [Thickness : um] 20 45 53 30 80 75 80 75 50 65 80 Extruded coating layer 2 PEEK PEE
  • the first extruded coating layer has a relative crystallinity of 45%
  • the second extruded coating layer has a relative crystallinity of 80%
  • the third level extruded coating layer has a relative crystallinity of 90%
  • Comparative Example 4 the adhesion strength between the thermosetting resin layer and the extruded coating layer was 115 gf/mm and the adhesion strength between the first extruded coating layer and the second extruded coating layer was greater than or equal to 300 gf/mm, and a crack extending from the second extruded coating layer and reaching the conductor occurred.
  • Comparative Example 5 the relative crystallinity of the first extruded coating layer was 80%, and, the adhesion strength between the thermosetting resin layer and the extruded coating layer was 40 gf/mm, and peeling occurred between the thermosetting resin layer and the extruded coating layer.
  • the resin of first extruded coating layer was PES and the resin of the second extruded coating layer was a polymer alloy of PES and PEEK, and the adhesion strength between the first extruded coating layer and the second extruded coating layer was 150 gf/mm, and a crack extending from the second extruded coating layer and reaching the conductor occurred, and, the ATF-resistant property was also poor.
  • the rectangular insulated wire of the present invention is preferably used as a magnet wire for motor coils installed in EV (electric vehicles) or HV (hybrid vehicles).

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Transportation (AREA)
  • Mechanical Engineering (AREA)
  • Insulated Conductors (AREA)
  • Insulation, Fastening Of Motor, Generator Windings (AREA)
  • Coils Of Transformers For General Uses (AREA)
  • Organic Insulating Materials (AREA)
  • Coils Or Transformers For Communication (AREA)
  • Insulating Of Coils (AREA)

Claims (6)

  1. Rechteckiger isolierter Draht (1), aufweisend:
    einen rechteckigen Leiter (2) mit einem im Allgemeinen rechteckigen Querschnitt;
    eine wärmehärtende Harzschicht (3), die zum Bedecken des rechteckigen Leiters (2) bereitgestellt ist; und
    eine Vielzahl von thermoplastischen Harzschichten (4, 5), die auf der wärmehärtenden Harzschicht (3) bereitgestellt sind,
    eine Adhäsionskraft zwischen der wärmehärtenden Harzschicht (3) und der thermoplastischen Harzschicht (4), die 50 gf/mm bis 100 gf/mm beträgt,
    dadurch gekennzeichnet, dass jede der Vielzahl der thermoplastischen Harzschichten (4, 5) aus kristallinem Harz besteht,
    wobei die wärmehärtende Harzschicht (3) aus einem oder mehreren Materialien gebildet ist, die ausgewählt aus der Gruppe ist, die aus Polyamidimid, Polyimid und Polyetherimid besteht.
  2. Rechteckiger isolierter Draht nach Anspruch 1, wobei die kristalline Harzschicht aus einem beliebigen Material gebildet ist, das aus der Gruppe ausgewählt ist, die aus Polyetheretherketon, Polyehterketonketon, Polyetherketon, Polyphyenlensulfid und thermoplastischem Polyimid besteht.
  3. Rechteckiger isolierter Draht nach Anspruch 1 oder 2, wobei die Adhäsionskräfte zwischen der Mehrzahl an thermoplastischen Harzschichten (4, 5) jeweils 50 gf/mm bis 100 gf/mm betragen.
  4. Rechteckiger isolierter Draht nach Anspruch 1, wobei die Mehrzahl an thermoplastischen Harzschichten (4,5) eine erste thermoplastische Harzschicht (4) und eine zweite thermoplastische Harzschicht (5) umfassen, die auf der ersten thermoplastischen Harzschicht (4) bereitgestellt sind.
  5. Rechteckiger isolierter Draht nach einem der Ansprüche 1 bis 3, wobei der rechteckige Leiter (2) eines aus Aluminium, Aluminiumlegierung, Kupfer und Kupferlegierung ist.
  6. Elektrische Generatorspule, die durch Wickeln des rechteckigen isolierten Drahtes nach einem der Ansprüche 1 bis 5 geformt ist.
EP14877820.2A 2014-01-10 2014-11-21 Rechteckiger isolierter draht und stromgeneratorspule Active EP3093854B1 (de)

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MY174326A (en) 2020-04-08
TWI667664B (zh) 2019-08-01
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EP3093854A1 (de) 2016-11-16
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